Nanoscale Helical Optical Force for Determining Crystal Chirality.

The deterministic control of material chirality has been a sought-after goal. As light possesses intrinsic chirality, light-matter interactions offer promising avenues for achieving non-contact, enantioselective optical induction, assembly, or sorting of chiral entities. However, experimental validations are confined to the microscale due to the limited strength of asymmetrical interactions within sub-diffraction limit ranges. In this study, a novel approach is presented to facilitate chirality modulation through chiral crystallization using a helical optical force field originating from localized nanogap surface plasmon resonance. The force field emerges near a gold trimer nanogap and is propelled by linear and angular momentum transfer from the incident light to the resonant nanogap plasmon. By employing Gaussian and Laguerre-Gaussian incident laser beams, notable enantioselectivity is achieved through low-power plasmon-induced chiral crystallization of an organic compound-ethylenediamine sulfate. The findings provide new insights into chirality transmission orchestrated by the exchange of linear and angular momentum between light and nanomaterials.

Enantioselective control in chiral crystallization of ethylenediamine sulfate using optical trapping with circularly polarized laser beams.

In this study, we conducted successful experiments on ethylenediamine sulfate (EDS), an organic compound, to investigate its enantioselectivity in chiral crystallization. We employed optical trapping with circularly polarized laser beams, using a continuous wave laser at 1064 nm. By focusing the laser at the air-solution interface of a heavy water-saturated EDS solution, the formation of sub-micrometer-sized chiral EDS crystals was verified. Two generated enantiomorphs (d-crystal and l-crystal) were identified by the rotating analyzer method. The enantioselectivity in the chiral crystallization of EDS was assessed through 30 to 60 times experiments conducted under various conditions of laser powers and polarization modes, utilizing the count of generated crystals for each enantiomorph in the evaluation. Circularly polarized lasers at a specific power created an imbalance in the generation probability of the enantiomorphs, resulting in crystal enantiomeric excess values of 23% and -30%. The enantioselectivity mechanism was explored from two perspectives: refractive index differences of two enantiomorphs and 3D helical optical forces. Study of the thermodynamic mechanism was insufficient to explain the outcomes. Conversely, the 3D helical optical force mechanism revealed that the forces acting on EDS clusters in solution induced helical fluid motion, driving EDS nucleation, with the helicity of fluid motion determining the crystal's chirality. This approach will present new insights into chirality in industrial and research fields, with potential applications in regard to improving optical resolution and addressing the origin of homochirality.

Unravelling 3D Dynamics and Hydrodynamics during Incorporation of Dielectric Particles to an Optical Trapping Site.

Mapping of the spatial and temporal motion of particles inside an optical field is critical for understanding and further improvement of the 3D spatio-temporal control over their optical trapping dynamics. However, it is not trivial to capture the 3D motion, and most imaging systems only capture a 2D projection of the 3D motion, in which the information about the axial movement is not directly available. In this work, we resolve the 3D incorporation trajectories of 200 nm fluorescent polystyrene particles in an optical trapping site under different optical experimental conditions using a recently developed widefield multiplane microscope (imaging volume of 50 × 50 × 4 µm3). The particles are gathered at the focus following some preferential 3D channels that show a shallow cone distribution. We demonstrate that the radial and the axial flow speed components depend on the axial distance from the focus, which is directly related to the scattering/gradient optical forces. While particle velocities and trajectories are mainly determined by the trapping laser profile, they cannot be completely explained without considering collective effects resulting from hydrodynamic forces.

Structural region essential for amyloid fibril formation in cytochrome c elucidated by optical trapping.

Amyloid fibril formation of cytochrome c is spatially and temporally controlled with a combined method of disulfide bond cross-linking of cysteine-introduced variants and optical trapping, identifying that the structural change in the region containing Ala83 is essential for the amyloid fibril formation.

The primeval optical evolving matter by optical binding inside and outside the photon beam.

Optical binding has recently gained considerable attention because it enables the light-induced assembly of many-body systems; however, this phenomenon has only been described between directly irradiated particles. Here, we demonstrate that optical binding can occur outside the focal spot of a single tightly focused laser beam. By trapping at an interface, we assemble up to three gold nanoparticles with a linear arrangement which fully-occupies the laser focus. The trapping laser is efficiently scattered by this linear alignment and interacts with particles outside the focus area, generating several discrete arc-shape potential wells with a half-wavelength periodicity. Those external nanoparticles inside the arcs show a correlated motion not only with the linear aligned particles, but also between themselves even both are not directly illuminated. We propose that the particles are optically bound outside the focal spot by the back-scattered light and multi-channel light scattering, forming a dynamic optical binding network.

Laser-Induced NanoKneading (LINK): Deformation of Patterned Azopolymer Nanopillar Arrays via Photo-Fluidization.

Ordered arrays of polymer nanostructures have been widely investigated because of their promising applications such as solar-cell devices, sensors, and supercapacitors. It remains a great challenge, however, to manipulate the shapes of individual nanostructures in arrays for tailoring specific properties. In this study, an effective strategy to prepare anisotropic polymer nanopillar arrays via photo-fluidization is presented. Azobenzene-containing polymers (azopolymers) are first infiltrated into the nanopores of ordered anodic aluminum oxide (AAO) templates. After the removal of the AAO templates using weak bases, azopolymer nanopillar arrays can be prepared. Upon exposure of linearly polarized lights, azobenzene groups in the azopolymers undergo trans-cis-trans photoisomerization, causing mass migration and elongation of the nanopillar along with the polarization directions. As a result, anisotropic nanopillar arrays can be fabricated, of which the deformation degrees are controlled by the illumination times. Furthermore, patterned nanopillar arrays can also be constructed with designed photomasks. This work presents a practical and versatile strategy to fabricate arrays of anisotropic nanostructures for future technical applications.

Anomalously Large Assembly Formation of Polystyrene Nanoparticles by Optical Trapping at the Solution Surface.

We demonstrated the optical trapping-induced formation of a single large disc-like assembly (∼50 µm in diameter) of polystyrene (PS) nanoparticles (NPs) (100 nm in diameter) at a solution surface. Different from the conventional trapping behavior in solution, the assembly grows from the focus to the outside along the surface and contains needle structures expanding radially in all directions. Upon switching off the trapping laser, the assembly disperses and needle structures disappear, while the highly concentrated domain of the NPs is left for a while. The single assembly is quickly restored by switching on the laser again, where the needle structures are also reproduced but in a different way. When a single 10 µm PS microparticle (MP) is trapped in the NP solution, a single disc-like assembly containing needle structures is similarly prepared outside the MP. Based on backscattering imaging and tracking analyses of the MP at the solution surface, it is proposed that scattering and propagation of the trapping laser from the central part of the NP assembly or the MP lead to this new phenomenon.

Surface plasmon resonance effect on laser trapping and swarming of gold nanoparticles at an interface.

Laser trapping at an interface is a unique platform for aligning and assembling nanomaterials outside the focal spot. In our previous studies, Au nanoparticles form a dynamically evolved assembly outside the focus, leading to the formation of an antenna-like structure with their fluctuating swarms. Herein, we unravel the role of surface plasmon resonance on the swarming phenomena by tuning the trapping laser wavelength concerning the dipole mode for Au nanoparticles of different sizes. We clearly show that the swarm is formed when the laser wavelength is near to the resonance peak of the dipole mode together with an increase in the swarming area. The interpretation is well supported by the scattering spectra and the spatial light scattering profiles from single nanoparticle simulations. These findings indicate that whether the first trapped particle is resonant with trapping laser or not essentially determines the evolution of the swarming.

Plasmonic Manipulation-Controlled Chiral Crystallization of Sodium Chlorate.

Plasmonic manipulation using well-designed triangular trimeric gold nanostructures achieves a giant (greater than 50%) crystal enantiomeric excess (CEE) of sodium chlorate (NaClO3). Stronger asymmetric interactions between molecule and light are pursued to reach high enantiomeric excess. The well-designed gold nanostructures immersed in a saturated NaClO3 D2O solution were irradiated with linear, left-hand, and right-hand circular polarizations of a 1064 nm continuous-wave laser. Within seconds of the start of the irradiation, an achiral metastable crystal was formed at the laser focus, and further irradiation induced a subsequent polymorphic transition to the chiral crystal. The crystal chirality is sensitive to the handedness of circular polarization, allowing for efficient enantioselectivity. The mechanisms to achieve this giant CEE are proposed based on the results of electromagnetic field analysis generated near the nanostructure by the finite element method.

Laser-Assisted Nanowetting: Selective Fabrication of Polymer/Gold Nanorod Arrays Using Anodic Aluminum Oxide Templates.

1D polymer nanomaterials have attracted significant interest in recent years because of their unique properties and promising applications in various fields. It is, however, still a challenge to fabricate polymer nanoarrays with desired sizes and controlled morphologies. Here, an unprecedented approach, the laser-assisted nanowetting (LAN) method, to selectively fabricate polymer nanoarrays is presented. Polystyrene (PS) is blended with gold nanorods (AuNRs), which are used to absorb the energy from the laser. After the blend films are brought in contact with AAO templates, the AuNRs at regions shone by the laser beams absorb the energy and heat the surrounding polymer chains, resulting in the formation of PS/AuNRs arrays in selected areas. This work paves a new research direction for developing template-based polymer nanomaterials.

Spatiotemporal Dynamics of Aggregation-Induced Emission Enhancement Controlled by Optical Manipulation.

We present spatiotemporal control of aggregation-induced emission enhancement (AIEE) of a protonated tetraphenylethene derivative by optical manipulation. A single submicrometer-sized aggregate is initially confined by laser irradiation when its fluorescence is hardly detectable. The continuous irradiation of the formed aggregate leads to sudden and rapid growth, resulting in bright yellow fluorescence emission. The fluorescence intensity at the peak wavelength of 540 nm is tremendously enhanced with growth, meaning that AIEE is activated by optical manipulation. Amazingly, the switching on/off of the activation of AIEE is arbitrarily controlled by alternating the laser power. This result means that optical manipulation increases the local concentration, which overcomes the electrostatic repulsion between the protonated molecules, namely, optical manipulation changes the aggregate structure. The dynamics and mechanism in AIEE controlled by optical manipulation will be discussed from the viewpoint of molecular conformation and association depending on the laser power.

Micromanipulation of amyloplasts with optical tweezers in Arabidopsis stems.

Intracellular sedimentation of highly dense, starch-filled amyloplasts toward the gravity vector is likely a key initial step for gravity sensing in plants. However, recent live-cell imaging technology revealed that most amyloplasts continuously exhibit dynamic, saltatory movements in the endodermal cells of Arabidopsis stems. These complicated movements led to questions about what type of amyloplast movement triggers gravity sensing. Here we show that a confocal microscope equipped with optical tweezers can be a powerful tool to trap and manipulate amyloplasts noninvasively, while simultaneously observing cellular responses such as vacuolar dynamics in living cells. A near-infrared (λ=1064 nm) laser that was focused into the endodermal cells at 1 mW of laser power attracted and captured amyloplasts at the laser focus. The optical force exerted on the amyloplasts was theoretically estimated to be up to 1 pN. Interestingly, endosomes and trans-Golgi network were trapped at 30 mW but not at 1 mW, which is probably due to lower refractive indices of these organelles than that of the amyloplasts. Because amyloplasts are in close proximity to vacuolar membranes in endodermal cells, their physical interaction could be visualized in real time. The vacuolar membranes drastically stretched and deformed in response to the manipulated movements of amyloplasts by optical tweezers. Our new method provides deep insights into the biophysical properties of plant organelles in vivo and opens a new avenue for studying gravity-sensing mechanisms in plants.

Spatiotemporal Dynamics of Laser-Induced Molecular Crystal Precursors Visualized by Particle Image Diffusometry.

We have succeeded in label-free visualization of spatiotemporal dynamics of laser-induced crystal precursors in aqueous solutions. The tracking-free evaluation of the diffusion-coefficient field for the observation domain with tens of micrometers on a side from microscopy movie data is realized by particle image diffusometry (PID). PID revealed the time fluctuation of coverage composition with the nonuniform space distribution of diffusion coefficients by the prenucleation clusters. Furthermore, the results indicate the existence of a loose aggregation domain of prenucleation clusters where the order of viscosity corresponds to that of honey.

Rapid localized crystallization of lysozyme by laser trapping.

Confining protein crystallization to a millimetre size was achieved within 0.5 h after stopping 1 h intense trapping laser irradiation, which shows excellent performance in spatial and temporal controllability compared to spontaneous nucleation. A continuous-wave near-infrared laser beam is tightly focused into a glass/solution interfacial layer of a supersaturated buffer solution of hen egg-white lysozyme (HEWL). The crystallization is not observed during laser trapping, but initiated by stopping the laser irradiation. The generated crystals are localized densely in a circular area with a diameter of a few millimetres around the focal spot and show specific directions of the optical axes of the HEWL crystals. To interpret this unique crystallization, we propose a mechanism that nucleation and the subsequent growth take place in a highly concentrated domain consisting of HEWL liquid-like clusters after turning off laser trapping.

Femtosecond-Laser-Enhanced Amyloid Fibril Formation of Insulin.

Femtosecond (fs)-laser-induced crystallization as a novel crystallization technique was proposed for the first time by our group, where the crystallization time can be significantly shortened under fs laser irradiation. Similarly, we have further extended our investigation to amyloid fibril formation, also known as a nucleation-dependence process. Here we demonstrate that the necessary time for amyloid fibril formation can be significantly shortened by fs laser irradiation, leading to favorable enhancement. The enhancement was confirmed by both spectral measurements and direct observations of amyloid fibrils. The thioflavin T fluorescence intensity of laser-irradiated solution increased earlier than that of the control solution, and such a difference was simultaneously revealed by ellipticity changes. At the same time before intensity saturation in fluorescence, the number of amyloid fibrils obtained under laser irradiation was generally more than that in the control solution. Besides, such an enhancement is correlated to the laser power threshold of cavitation bubbling. Possible mechanisms are proposed by referring to fs-laser-induced crystallization and ultrasonication-induced amyloid fibril formation.

A Single Spherical Assembly of Protein Amyloid Fibrils Formed by Laser Trapping.

Protein amyloids have received much attention owing to their correlation with serious diseases and to their promising mechanical and optical properties as future materials. Amyloid formation has been conducted by tuning temperature and chemical conditions, so that its nucleation and the following growth are analyzed as ensemble dynamics. A single spherical assembly of amyloid fibrils of cytochrome c domain-swapped dimer was successfully generated upon laser trapping. The amyloid fibrillar structure was confirmed by fluorescence characterization and electron microscopy. The prepared spheres were further manipulated individually in solution to fabricate a three-dimensional microstructure and a line pattern. Amyloid formation dynamics and amyloid-based microstructure fabrication are demonstrated based on direct observation of a single spherical assembly, which foresees a new approach in amyloid studies.

Optically Evolved Assembly Formation in Laser Trapping of Polystyrene Nanoparticles at Solution Surface.

Assembling dynamics of polystyrene nanoparticles by optical trapping is studied with utilizing transmission/reflection microscopy and reflection microspectroscopy. A single nanoparticle assembly with periodic structure is formed upon the focused laser irradiation at solution surface layer and continuously grows up to a steady state within few minutes. By controlling nanoparticle and salt concentrations in the colloidal solution, the assembling behavior is obviously changed. In the high concentration of nanoparticles, the assembly formation exhibits fast growth, gives large saturation size, and leads to dense packing structure. In the presence of salt, one assembly with the elongated aggregates was generated from the focal spot and 1064 nm trapping light was scattered outwardly with directions, while a small circular assembly and symmetrical expansion of the 1064 nm light were found without salt. The present nanoparticle assembling in optical trapping is driven through multiple scattering in gathered nanoparticles and directional scattering along the elongated aggregates derived from optical association of nanoparticles, which dynamic phenomenon is called optically evolved assembling. Repetitive trapping and release processes of nanoparticles between the assembly and the surrounding solution always proceed, and the steady state at the circular assembly formed by laser trapping is determined under optical and chemical equilibrium.

Laser trapping-induced crystallization of L-phenylalanine through its high-concentration domain formation.

We present the laser trapping-induced crystallization of L-phenylalanine through high-concentration domain formation in H2O and D2O solutions which is achieved by focusing a continuous-wave (CW) near-infrared laser beam at the solution surface. Upon laser irradiation into the H2O solution, laser trapping of the liquid-like clusters increases the local concentration, accompanying laser heating, and a single plate-like crystal is eventually prepared at the focal spot. On the other hand, in the D2O solution, a lot of the monohydrate needle-like crystals are observed, not at the focal spot where the concentration is high enough to trigger crystal nucleation, but in the 0.5-1.5 mm range from the focal spot. The dynamics and mechanism of the amazing crystallization behaviour induced by laser trapping are discussed from the viewpoints of the concentration increase due to laser heating depending on solvent, the large high-concentration domain formation by laser trapping of liquid-like clusters, and the orientational disorder of molecules/clusters at the domain edge.

Laser Trapping and Crystallization Dynamics of l-Phenylalanine at Solution Surface.

We present laser trapping behavior of l-phenylalanine (l-Phe) at a surface of its unsaturated aqueous solution by a focused continuous-wave (CW) near-infrared (NIR) laser beam. Upon the irradiation into the solution surface, laser trapping of the liquid-like clusters is induced concurrently with local laser heating, forming an anhydrous plate-like crystal at the focal spot. The following laser irradiation into a central part of the plate-like crystal leads to laser trapping at the crystal surface not only for l-Phe molecules/clusters but also for polystyrene (PS) particles. The particles are closely packed at crystal edges despite that the crystal surface is not illuminated by the laser directly. The molecules/clusters are also gathered and adsorbed to the crystal surface, leading to crystal growth. The trapping dynamics and mechanism are discussed in view of optical potential formed at the crystal surface by light propagation inside the crystal.